Abstract

A synergistic Rh(II)/Pd(0) dual-catalyzed strategy that enabled three-component oxy-allylation of α-diazo esters, alcohols, and allylic benzoates was described. Trapping of active protic oxonium ylides with catalytic π-allyl Pd(II) intermediates was proposed for this reaction. More strikingly, water was also a suitable partner in this reaction involving a different allylic migratory insertion of palladium-carbenes. These transformations provided straightforward access to various α-ternary allylated carboxylic esters using simple and readily available starting materials under redox-neutral conditions, in which two new CO and CC bonds were generated successively at the carbene center.

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